Azo dyestuffs



Patented Apr. 11, 1933 UNITED STATES nueo scHwEiTzER, F. LEVERKUSEN-W'IESDORF, GERMANY, A-SSIGNOR- To GENERAL ANILII IE WORKS, INC., OF NEW.YORK,'N. Y A CORPORATION OF DELAWARE AZO nyns'rurr's No Drawing. Application filed May 11, 1931, semi n'o. 536,664, and in Germany May 24, 1930.

-J in which-z and onew stand for a sulfonamide group, the hydrogen atoms of which may be partially or wholly substituted by alkyl or a radical of the benzene series, the-other w stands for hydrogen, y stands for hydrogen which in case them in the 6-position of the naphthalene nucleus stands for a 'sulfonamlde group may be substituted by halogen or a sulfonamide group the hydrogen atoms of which may be substituted by alkyl or a radical of the benzene series, and R stands. for a benzene or naphthalene nucleus containing at least one sulfonic acid group and which may be otherwise substituted by monovalent substituents, for example, by alkyl, alkoxy, halogen, the nitro-group, I an acylamlno group and the hydroxy group.

My new dyestuffs are obtainable by coupling in aqueous alkaline solution a diazotized amino-sulfonic acid of the benzene or naphthalene series with a 1-naphthol-3.6- or 3.7 -disulfonic acid amide or an N-alkyl or phenyl substitution product thereof which naphthol-3.6-disulf0nic acid amide may be substituted in the 8-posit-ion by halogen or a further sulfonamide group the hydrogen atoms of which may be substituted by alkyl or a radical of the benzene series.

The new dyestuffs are in form of their alkali metal salts generally water soluble dark substances, soluble in concentrated sulfuric acid with a red to bluish-violet coloration,- and dyeing wool from an acid bath clear red to blue shades which are distinguished by a good fastness to light, very good fastness to washin 'pacity for even dyeing. They are also very suitable for the manufacture of'color lakes 7 and for printing.

The invention is illustrated by the followand fulling and unobjectionable caing examples, without being limited thereto:

Example 1.17.3 parts'by-weight ofaniline-Q-sulfonic acid are diazotized in the customary manner. The dlazo compound is run into a sodium carbonate solution of 48,2 parts by weight of 1-naphtl1ol 3.6 disulfonic aciddi-(N-methylanilide). When the coupling is complete the dyestufi which has in its free state the following formula 1 SIOaH 1 is salted out, filtered with suction and dried. It dyes wool a clear orange of good fastness to fulling and light and good evenness.

.W hen the aniline 2-sulfonic acid is replaced by et-methoxyEI-aminobenzene-Q-sulfonic acid or by 4-methyl-1-aniinobenzene-Q- sulfonic acid or by 4-acetylamino-1-amino-' benzene-Q-sulfonic acid bluish red shades of similar properties result. EwampZe2=+18.7'partsbyweightof i-methyl-l-aminobenzene- 2 -sulfonic acid are diazotized in the customary manner. The diazo compound is run into a sodium carbonate solution of 454 parts by weight of 1-naphthol-3.6 disulfonic acid-di-anilide. When the coupling is complete thedyestufi having in its free state the following formula:

ruc S0311 IIIH dyes wool a yellowish red of good fastness to fulling and light and good evenness.

When the t-methyl-l-aminobenzene-Q-sulfonic acid is replaced by other amino-sulfonic acids of the benzene series and the l-naphthol-3.6-disulfonic acid-di-(anilide) by corresponding chloroanilides, tolu'idides and the like dyestuffs of similar properties result.

Example 3.-20.7 parts by Weight of 4- chloro-1-aminobenzene-2-sulfonio acid are diazotized in the customary manner. The

naphthol-3.6-disulfo diamide or the l-naphthol-3.6-disulfo-methylamide dyestuffs of similar properties result.

Example 5.20.1 parts by Weight of mxylidine-o-sulfonic acid are diazotized in the customary manner. The diazo compound is run into asodium carbonate solution of 56.8 parts by Weight of 1-naphthol-3.6-disulfonic its free state the following formula:

diazo compound is run into a sodium carbon ate solution of 54.5 parts by Weight of 1- naphthol-3.6-disulfonic acid-di- (N-hydroxyr ethylanilide). When the coupling is complete the dyestuff having in its free state the following formula:

OHrOHa-OH 1 N-CHz-CHg-OH is worked up in the customary manner. It dyes wool a yellowish red. The very even dyeing is fast to light and fulling.

7 When the chloro-1-aminobenzenee2-sulfoni'o acid is replaced by other amino-sul- V fonic acids-of the benzene series, such as for example,- l amino acetanilide 3 sulfonic acid,' 4-methyl-1-amino-benzene-2-sulfonic acid or the like dyestufl's of similar properties result.

Example 4.1-8.7 parts by weight of 4- methyl-l-aminobenzene-Q-sulfonic acid are diazotized in the customary manner. The diazo compound is run intosoda alkalinesolution of 24.2 parts by weight of 1-naphthol- 3.6-disulfo-di-dimethylamide. When the coupling is complete, the dyestufi' having in its free state the following formula:

is worked up in the usual manner. It dyes wool a red of good fastnessjto fulling and light and good evenness.

When the -methyl-l-aminobenzene-Q-sulfonio acid is replaced by other aminosulfonic acids of the benzene series and the l-naphthol-3.6-d isulfo-di-dimethylamide by CH3 0H 0 oil 9'10: NH NH GHa-CO-NH- ONE-CODE:

' isworked up in the known manner.

Itydyes wool a clear yellowish red of Very good .fastness to fulling and light besides very 'good'evenness. When the l-nap'hthol- 3.6- disulfonic acid-di-(3'-acetylamino-anilide) is replaced by l-naphthol-3.6-disulfonic acid-di- (4J-acetylaminoanilide) or the 4-methyl-Laminobenzene-Qesulfonic acid by other amino sul-fonic acids of the benzene series dyestuffs of similar properties result,

Example 62-18.? parts by weight of 4- methyl-l-aminobenzene-Q-sulfonic acid are d-iazotized in the customary manner. The diazo compound is run into a sodium carbonate solution of 48.8 parts by weight of 8-.chloro-1-naphtho-l-3.6-disulfonic When the coupling is complete the dyestufi having in itsffree state the following formula:

acid-dianilide.

aciddi-(3'-acetylaminoanilide). When the coupling is complete the dyestufl having in thecoupling is complete the dyestuff having in its free state the following formula:

is salted out, filtered, pressed and dried.

HaQ

I om-oo-NH 1 t NH NH CH;-CO-HN NH OO-CHa is salted out, filtered, pressed and dried It dyes wool a clear violet, fast to washing and fulling and of very good evenness.

When the 1-naphthol-3.6-disulfonic acid di- (3-acetylamino-anilide) is replaced by 1 3 naphthol-3L6-disulfonic acid-di-'(4-acetylam inoanilide) a dyestufl ofsimilar properties results. I V i ff: Example 95-23 parts by weight of 4 acetylamino-l-amino-benzene-2 sulfonic acid are diazotized and the diazo compound is added to a solution-rendered alkalinewith sodium carbonate of 45.4 parts by weight-of 1 naphthol 3.7 disulfonic acid '-.dianilide. When the coupling is complete the dyestufl having in its free state the following formula:

is isolated inthe usual way. o It dyes wool a bluish-redof good fastness to light, washing and fulling and good even,-

ness.

v l The l-acetylamino-l-aminObenZene-Q sulfonic acid can be replaced by other aminosulfonic acids of thebenzene series; the 1- naphthol-3.7-disulfoni acid dianilide can be replaced by.the 3.7-disulfonic aciddi- (3- acetylaminoanilide) or other anilide'sj Dyes of similar properties are thus obtained. i

I claim:

1. Azodyestufis of the probable general formula:

1/. OH 7 I wherein and one stand for a'sulfonaniide group, the hydrogen atoms'of which may besubstituted. by alkyl or a radical of-the beIi-'- zene series, the other 00 stands for hydrogen,-

y stands for hydrogen which in case the w in the fi-position of the naphthalene nucleus stands for a sulfonamide group may be sub-' stituted by halogen or a sulfonamide group the hydrogen atoms of which may be substituted by alkyl or a radical ofthe benzene series, andR stands fora benzene or naphthalene nucleus,conta1n1ng at least one sul-- fonic acid group and which nucleus may be otherwise substituted by substituents of the group consisting of alkyl, alkoxy, halogen, an acylamino group, the hydroxy-group and the nitro group, being in form oftheir alkali metal salts generally water soluble dark substances, soluble in concentrated sulfuric acid with a red to bluish-violet coloration and dyeing wool from an acid bath clear red to blue shades which are distinguished by a good fastness to light, washing and fulling.

2. Azodyestufl's of the probable general formula:

wherein 2; stands for hydrogen, alkyl or a radical of the benzene series,' z stands for hydrogen, halogen or a sulfonamide group, the hydrogen atoms of which may be substituted .by alkyl or a radical of the benzene series wherein 2 stands for alkyl or a radical of the benzene series andR stands for a benzene nucleus containing .at least one sulfonic acid group and which nucleus may beotherwise substituted by alkyl, alkoxy, halogen,- an acylamino group, the hydroxy group and the nitro group, being in form of their alkali metal salts generally water soluble dark substances, soluble in concentrated sulfuric acid with a-red to bluish-violet coloration and dye ing wool from an acid bath clear red to blue shades which are distinguished by a good fastnessto light, washing and fulling.

4c.v The azodyestuff of the following formula: I

dyeing wool a yellowish red of good fastness to light and fulling.

5. The azodyestuf'f of the following formula: s

0H OHM;

CH3 1130 SOaH soN SIC: 0113 N 1130 om dyeing wool a red shade of good fastness to fulling and light.

In testimony whereof, I affix my signature.

HUGO SGHWEITZER. 

